Functionalized Esters, Amides or Urethanes of Perfluorinated Alcohols or Amines as Surface Modifiers

ABSTRACT

The invention describes a composition comprising a) an organic material which is susceptible to oxidative, thermal or light-induced degradation, and b) at least one melt additive of a compound of the formula I R1 (I) R3 X R2 wherein the general symbols are as defined in claim  1 . The compounds of the formula I are useful as reducers of surface energy for organic materials, for example, for increasing the oil and water repellency of organic materials.

The present invention relates to compositions comprising an organicmaterial, preferably a synthetic polymer, susceptible to oxidative,thermal or light-induced degradation and to esters, amides or urethanesof perfluorinated alcohols as reducer of surface energy of thesematerials, for example as oil and water repellency agents for organicmaterials.

The use of various fluorochemical compositions on fibers and fibroussubstrates, such as for example textiles, carpets, paper, leather andnon-woven webs to impart oil and water repellency is known for examplein U.S. Pat. No. 6,127,485. This reference discloses hydrophobic andoleophobic fibers, films and molded articles comprising syntheticorganic polymer wherein dispersed within the fiber, fabric or moldedarticle and present at the surface of the fiber, fabric or moldedarticle are fluorochemical compounds.

The known fluorochemicals do not satisfy in every respect the highrequirements which a melt additive is required to meet as reducers ofsurface energy for organic materials, for example, for increasing theoil and water repellency of organic materials.

It has now been found that esters, amides or urethanes of perfluorinatedalcohols are useful for various technical applications such as forexample for increasing the oil and water repellency of organic materialslike for example synthetic polymers.

The present invention therefore provides a composition comprising

-   -   a) an organic material which is susceptible to oxidative,        thermal or light-induced degradation, and    -   b) at least a compound of the formula I

-   -   wherein    -   R₁ is —NO₂, —N═CH—R₄ or

-   -   R₂ is —NO₂, —N═CH—R₄,

-   -   R₃ is a fluorine containing group,    -   R₄ is C₁-C₂₅alkyl, C₃-C₂₅alkenyl, unsubstitued or C₁-C₄alkyl        substituted phenyl;    -   R₅ is hydrogen, —Y—R₇,

-   -   R₆ is hydrogen, C₁-C₈alkyl or benzyl,    -   R₇ is C₁-C₂₅alkyl, C₂-C₂₅alkenyl, unsubstitued or with        C₁-C₄alkyl or C₁-C₄alkanoylamino substituted phenyl;        unsubstituted or C₁-C₄alkyl substituted phenylamino;    -   R₈ is —NO₂, —N═CH—R₄ or

-   -   R₉ is hydrogen or —Y—R₇,

-   -   R₁₀ is hydrogen, C₁-C₈alkyl or benzyl,    -   X is

-   -   R₁₁ is hydrogen, C₁-C₈alkyl or benzyl,    -   Y is

-   -   Z is C₁-C₂₅alkylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene        or

and

-   -   R₁₂ and R₁₃ are each independently of one another hydrogen,        C₁-C₁₂alkyl or phenyl, or R₁₁ and R₁₂ together with the linking        carbon atom, form a C₅-C₈cycloalkylidene ring which is        unsubstituted or substituted by 1 to 3 C₁-C₄alkyl groups.

A fluorine containing group is a branched or unbranched radical, whichcontains at least one fluoro atom, for example C₁-C₂₅fluoroalkyl,C₁-C₂₅fluoroalkyl is for example fluoromethyl, 2-fluoroethyl,3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl,7-fluoroheptyl, difluoromethyl, trifluoromethyl, pentafluoroethyl,pentafluorobutyl or perfluoroalkyl such as for example —CH₂CH₂(CF₂)₇CF₃or —CH₂CH₂(CF₂)₃CF₃.

Alkyl having up to 25 carbon atoms is a branched or unbranched radical,for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,icosyl or docosyl.

Alkenyl having 3 to 25 carbon atoms is a branched or unbranched radicalsuch as, for example, propenyl, 2-butenyl, 3-butenyl, isobutenyl,n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl,iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference isgiven to alkenyl having 3 to 18, especially 3 to 12, for example 3 to 6,especially 3 to 4 carbon atoms.

C₁-C₄Alkyl-substituted or C₁-C₄alkanoylamino substituted phenyl, whichcontains preferably from 1 to 3, especially 1 or 2, alkyl oralkanoylamino groups, is, for example, o-, m- or p-methyl phenyl,2,3-dimethylphenyl, 2,4-dimethyl phenyl, 2,5-dimethyl phenyl,2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl,2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 4-tert-pivaloylaminophenyl,2-ethylphenyl or 2,6-diethylphenyl.

C₁-C₄Alkyl-substituted phenylamino, which contains preferably from 1 to3, especially 1 or 2, alkyl groups, is, for example, o-, m- orp-methylphenylamino, 2,3-dimethylphenylamino, 2,4-dimethylphenylamino,2,5-dimethylphenylamino, 2,6-dimethylphenylamino,3,4-dimethylphenylamino, 3,5-dimethylphenylamino,2-methyl-6-ethylphenylamino, 4-tert-butylphenylamino, 2-ethylphenylaminoor 2,6-diethylphenylamino.

Alkanoylamino having up to 4 carbon atoms is a branched or unbranchedradical, for example formylamino, acetylamino, propionylamino,butanoylamino or pivaloylamino.

A C₅-C₈cycloalkylidene ring substituted by C₁-C₄alkyl, which containspreferably from 1 to 3, especially 1 or 2, branched or unbranched alkylgroup radicals, is, for example, cyclopentylidene,methylcyclopentylidene, dimethylcyclopentylidene, cyclohexylidene,methylcyclohexylidene, dimethylcyclohexylidene,trimethylcyclohexylidene, tertbutylcyclohexylidene, cycloheptylidene orcyclooctylidene. Preference is given to cyclohexylidene andtert-butylcyclohexylidene.

Interesting compositions comprise as component (b) at least a compoundof the formula I wherein

R₂ is —X—R₃,

R₃ is C₁-C₂₅fluoroalkyl,

X is

and

R₁₁ is hydrogen or C₁-C₄alkyl.

Preferred compositions comprise as component (b) at least a compound ofthe formula I wherein R₃ is C₁-C₂₅fluoroalkyl.

Preference is also given to compositions comprising as component (b) atleast a compound of the formula I wherein R₆ and R₁₀ are hydrogen.

Particular preference is given to compositions comprising as component(b) at least a compound of the formula I wherein R₇ is C₁-C₁₈alkyl,C₂-C₁₈alkenyl, unsubstitued or with C₁-C₄alkyl or C₁-C₄alkanoylaminosubstituted phenyl; unsubstituted or C₁-C₄alkyl substituted phenylamino.

Of interest are compositions comprising as component (b) at least acompound of the formula I wherein R₁₂ and R₁₃ are each independently ofone another hydrogen or C₁-C₄alkyl, or R₁₂ and R₁₃ together with thelinking carbon atom, form a cyclohexylidene ring.

Also of interest are compositions comprising as component (b) at leastone compound of the formula I, wherein

R₁ is —NO₂, —N═CH—R₄ or

R₂ is —NO₂, —N═CH—R₄,

or —X—R₃,

R₃ is —CH₂CH₂(CF₂)₇CF₃ or —CH₂CH₂(CF₂)₃CF₃,

R₄ is C₄-C₁₂alkyl, C₄-C₁₂alkenyl, unsubstitued or C₁-C₄alkyl substitutedphenyl;

R₅ is hydrogen, —Y—R₇,

R₆ is hydrogen,

R₇ is C₁-C₈alkyl, C₂-C₈alkenyl, phenyl or phenylamino,

R₈ is —NO₂, —N═CH—R₄ or

R₉ is hydrogen, —Y—R₇,

R₁₀ is hydrogen,

X is

R₁₁ is hydrogen,

Y is

Z is C₄-C₁₂alkylene, 1,3-phenylene, 1,4-phenylene or

and

R₁₂ and R₁₃ are hydrogen.

The compounds of the formula I can be prepared in per se known manner,for example by esterification or amidation of a carboxylic acid with analcohol or amide. The urethanes are preferably prepared by the reactionof an isocyanate with an alcohol.

The compounds of the formula I are suitable as oil and water repellencyagents for organic materials. Examples of organic materials which may bepresent in the compositions of the invention are following materials:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymersof cycloolefins, for instance of cyclopentene or norbornene,polyethylene (which optionally can be crosslinked), for example highdensity polyethylene (HDPE), high density and high molecular weightpolyethylene (HDPE-HMW), high density and ultrahigh molecular weightpolyethylene (HDPE-UHMW), medium density polyethylene (MDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either τ- or σ-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers(e.g. ethylene/norbornene like COC), ethylene/1-olefins copolymers,where the 1-olefin is generated in-situ; propylene/butadiene copolymers,isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acidcopolymers and their salts (ionomers) as well as terpolymers of ethylenewith propylene and a diene such as hexadiene, dicyclopentadiene orethylidene-norbornene; and mixtures of such copolymers with one anotherand with polymers mentioned in 1) above, for examplepolypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetatecopolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA),LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbonmonoxide copolymers and mixtures thereof with other polymers, forexample polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

Homopolymers and copolymers from 1.)-4.) may have any stereostructureincluding syndiotactic, isotactic, hemi-isotactic or atactic; whereatactic polymers are preferred. Stereoblock polymers are also included.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromaticmonomers including styrene, α-methylstyrene, all isomers of vinyltoluene, especially p-vinyltoluene, all isomers of ethyl styrene, propylstyrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, andmixtures thereof. Homopolymers and copolymers may have anystereostructure including syndiotactic, isotactic, hemi-isotactic oratactic; where atactic polymers are preferred. Stereoblock polymers arealso included.

6a. Copolymers including aforementioned vinyl aromatic monomers andcomonomers selected from ethylene, propylene, dienes, nitriles, acids,maleic anhydrides, maleimides, vinyl acetate and vinyl chloride oracrylic derivatives and mixtures thereof, for example styrene/butadiene,styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkylmethacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkylmethacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methylacrylate; mixtures of high impact strength of styrene copolymers andanother polymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

6b. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6.), especially includingpolycyclohexylethylene (PCHE) prepared by hydrogenating atacticpolystyrene, often referred to as polyvinylcyclohexane (PVCH).

6c. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure includingsyndiotactic, isotactic, hemi-isotactic or atactic; where atacticpolymers are preferred. Stereoblock polymers are also included.

7. Graft copolymers of vinyl aromatic monomers such as styrene orα-methylstyrene, for example styrene on polybutadiene, styrene onpolybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styreneand acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,acrylonitrile and methyl methacrylate on polybutadiene; styrene andmaleic anhydride on polybutadiene; styrene, acrylonitrile and maleicanhydride or maleimide on polybutadiene; styrene and maleimide onpolybutadiene; styrene and alkyl acrylates or methacrylates onpolybutadiene; styrene and acrylonitrile on ethylene/propylene/dieneterpolymers; styrene and acrylonitrile on polyalkyl acrylates orpolyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadienecopolymers, as well as mixtures thereof with the copolymers listed under6), for example the copolymer mixtures known as ABS, MBS, ASA or AESpolymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate

(PAN) and polyhydroxybenzoates, as well as block copolyether estersderived from hydroxyl-terminated polyethers; and also polyestersmodified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

29. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

Preferred organic materials are natural, semi-synthetic or, preferably,synthetic polymers.

Particularly referred organic materials are synthetic polymers, mostpreferably thermoplastic polymers. Especially preferred organicmaterials are polyacetals, polyolefins such as polypropylene orpolyethylene, polyether/polyurethanes, polyesters such as polybutyleneterephthalate, polycarbonates or polyamides.

To be singled out for special mention is the efficacy of the compoundsof the formula I [component (b)] as reducers of surface energy of theorganic materials. Organic materials with low surface energy haveintrinsically better properties like for example water and oilrepellency, hydrophobicity, barrier properties, easy to clean, selfcleaning, antigraffiti or solvent resistance.

The compounds of the formula I will preferably be added to the organicmaterial in concentrations of 0.01 to 10%, preferably 0.01 to 2%,typically 0.1 to 2%, based on the weight of said material.

In addition to components (a) and (b), the compositions of the inventionmay comprise further additives, such as for example the following:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutyl phenol, 2,6-dicyclopentyl-4-methyl phenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethyl phenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methyl phenol), 4,4′-thiobis(3,6-di-sec-amylphenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.

1.6. Alkylidenebisphenols, for example 2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methyl phenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methyllenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methyl phenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methyl phenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methyl phenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethyl benzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl)isocyanurate,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or poly-hydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1, supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyidiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyidiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenyl methane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide,bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octylatedN-phenyl-1-naphthylamine, a mixture of mono- and dialkylatedtert-butyl/tert-octyidiphenylamines, a mixture of mono- and dialkylatednonyidiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octyl-phenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene.

2. UV Absorbers and Light Stabilizers

2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tertbutyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂—]₂, whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-yl phenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)-phenyl]benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, for example4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butyl phenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate,N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, neopentyltetra(α-cyano-β,β-diphenylacrylate.

2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tertoctylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); a condensate of 1,6-hexanediamine and2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,a diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, areaction product of maleic acid anhydride-α-olefin copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine,2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine,1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,5-(2-ethyl hexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor(Clariant; CAS Reg. No. 106917-31-1],5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, thereaction product of2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s-triazinewith N,N′-bis(3-aminopropyl)ethylenediamine),1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazine-3-one-4-yl)amino)-s-triazine,1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazine-3-one-4-yl)amino)-s-triazine.

2.7. Oxamides, for example 4, 4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydro-oxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxyphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-dicumylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

5. Hydroxylamines, for example N,N-dibenzyl hydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine,N,N-ditetradecyl hydroxylamine, N,N-dihexadecylhydroxylamine,N,N-dioctadecyl hydroxylamine, N-hexadecyl-N-octadecylhydroxy-ylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenylnitrone,N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptyinitrone,N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecyl nnitrone,N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecyl nitrone,N-ocatadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-hepta-decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

7. Thiosynergists, for example dilauryl thiodipropionate, dimistrylthiodipropionate, distearyl thiodipropionate or distearyl disulfide.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecyl mercapto)propionate.

9. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.

11. Nucleating agents, for example inorganic substances, such as talcum,metal oxides, such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds, such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds, such as ioniccopolymers (ionomers). Especially preferred are1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyldibenzylidene)sorbitol, and1,3:2,4-di(benzylidene)sorbitol.

12. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

13. Other additives, for example plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611;DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP-A-1291384 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxylphenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl benzofuran-2-one,3-(2,3-dimethyl phenyl)-5,7-d i-tert-butyl benzofuran-2-one,3-(2-acetyl-5-isooctyl phenyl)-5-isooctylbenzofuran-2-one.

The further additives are typically used in concentrations of 0.01 to10%, based on the total weight of the material to be treated.

Preferred compositions of the invention comprise, as other additivesphenolic antioxidants, light stabilizers and/or processing stabilizers.

Incorporation of component (b) and, if desired, further additives intothe synthetic polymers is carried out by known methods, for examplebefore or during moulding or else by applying the dissolved or dispersedcompounds to the synthetic polymer, if appropriate with subsequent slowevaporation of the solvent.

The present invention also relates to a composition in the form of amasterbatch or concentrate comprising component (a) in an amount of from5 to 90% and component (b) in an amount of from 5 to 80% by weight.

Component (b) and, if desired, further additives, can also be addedbefore or during polymerisation or before crosslinking.

Component (b), with or without further additives, can be incorporated inpure form or encapsulated in waxes, oils or polymers into the syntheticpolymer. Component (b), with or without further additives, can also besprayed onto the synthetic polymer. It is able to dilute other additives(for example the conventional additives indicated above) or their meltsso that they too can be sprayed together with these additives onto thepolymer. Addition by spraying on during the deactivation of thepolymerization catalysts is particularly advantageous, it being possibleto carry out spraying using, for example, the steam used fordeactivation.

In the case of spherically polymerized polyolefins it may, for example,be advantageous to apply component (b), with or without other additives,by spraying.

The synthetic polymers prepared in this way can be employed in a widevariety of forms, for example as foams, films, fibres, tapes, mouldingcompositions, as profiles or as binders for coating materials,especially powder coatings, adhesives, putties or especially asthick-layer polyolefin mouldings which are in long-term contact withextractive media, such as, for example, pipes for liquids or gases,films, fibres, geomembranes, tapes, profiles or tanks.

The preferred thick-layer polyolefin mouldings have a layer thickness offrom 1 to 50 mm, in particular from 1 to 30 mm, for example from 2 to 10mm.

The compositions according to the invention can be advantageously usedfor the preparation of various shaped articles. Examples are:

I-1) Floating devices, marine applications, pontoons, buoys, plasticlumber for decks, piers, boats, kayaks, oars, and beach reinforcements.

I-2) Automotive applications, in particular bumpers, dashboards,battery, rear and front linings, moldings parts under the hood, hatshelf, trunk linings, interior linings, air bag covers, electronicmoldings for fittings (lights), panes for dashboards, headlamp glass,instrument panel, exterior linings, upholstery, automotive lights, headlights, parking lights, rear lights, stop lights, interior and exteriortrims; door panels; gas tank; glazing front side; rear windows; seatbacking, exterior panels, wire insulation, profile extrusion forsealing, cladding, pillar covers, chassis parts, exhaust systems, fuelfilter/filler, fuel pumps, fuel tank, body side mouldings, convertibletops, exterior mirrors, exterior trim, fasteners/fixings, front endmodule, glass, hinges, lock systems, luggage/roof racks, pressed/stampedparts, seals, side impact protection, sound deadener/insulator andsunroof.

I-3) Road traffic devices, in particular sign postings, posts for roadmarking, car accessories, warning triangles, medical cases, helmets,tires.

I-4) Devices for plane, railway, motor car (car, motorbike) includingfurnishings.

I-5) Devices for space applications, in particular rockets andsatellites, e.g. reentry shields.

I-6) Devices for architecture and design, mining applications, acousticquietized systems, street refuges, and shelters.

II-1) Appliances, cases and coverings in general and electric/electronicdevices (personal computer, telephone, portable phone, printer,television-sets, audio and video devices), flower pots, satellite TVbowl, and panel devices.

II-2) Jacketing for other materials such as steel or textiles.

II-3) Devices for the electronic industry, in particular insulation forplugs, especially computer plugs, cases for electric and electronicparts, printed boards, and materials for electronic data storage such aschips, check cards or credit cards.

II-4) Electric appliances, in particular washing machines, tumblers,ovens (microwave oven), dish-washers, mixers, and irons.

II-5) Covers for lights (e.g. street-lights, lamp-shades).

II-6) Applications in wire and cable (semi-conductor, insulation andcable-jacketing).

II-7) Foils for condensers, refrigerators, heating devices, airconditioners, encapsulating of electronics, semi-conductors, coffeemachines, and vacuum cleaners.

III-1) Technical articles such as cogwheel (gear), slide fittings,spacers, screws, bolts, handles, and knobs.

III-2) Rotor blades, ventilators and windmill vanes, solar devices,swimming pools, swimming pool covers, pool liners, pond liners, closets,wardrobes, dividing walls, slat walls, folding walls, roofs, shutters(e.g. roller shutters), fittings, connections between pipes, sleeves,and conveyor belts.

III-3) Sanitary articles, in particular shower cubicles, lavatory seats,covers, and sinks.

III-4) Hygienic articles, in particular diapers (babies, adultincontinence), feminine hygiene articles, shower curtains, brushes,mats, tubs, mobile toilets, tooth brushes, and bed pans.

III-5) Pipes (cross-linked or not) for water, waste water and chemicals,pipes for wire and cable protection, pipes for gas, oil and sewage,guttering, down pipes, and drainage systems.

III-6) Profiles of any geometry (window panes) and siding.

III-7) Glass substitutes, in particular extruded plates, glazing forbuildings (monolithic, twin or multiwall), aircraft, schools, extrudedsheets, window film for architectural glazing, train, transportation,sanitary articles, and greenhouse.

III-8) Plates (walls, cutting board), extrusion-coating (photographicpaper, tetrapack and pipe coating), silos, wood substitute, plasticlumber, wood composites, walls, surfaces, furniture, decorative foil,floor coverings (interior and exterior applications), flooring, duckboards, and tiles.

III-9) Intake and outlet manifolds.

III-10) Cement-, concrete-, composite-applications and covers, sidingand cladding, hand rails, banisters, kitchen work tops, roofing, roofingsheets, tiles, and tarpaulins.

IV-1) Plates (walls and cutting board), trays, artificial grass,astroturf, artificial covering for stadium rings (athletics), artificialfloor for stadium rings (athletics), and tapes.

IV-2) Woven fabrics continuous and staple, fibers (carpets/hygienicarticles/geotextiles/monofilaments; filters; wipes/curtains(shades)/medical applications), bulk fibers (applications such asgown/protection clothes), nets, ropes, cables, strings, cords, threads,safety seat-belts, clothes, underwear, gloves; boots; rubber boots,intimate apparel, garments, swimwear, sportswear, umbrellas (parasol,sunshade), parachutes, paraglides, sails, “balloon-silk”, campingarticles, tents, airbeds, sun beds, bulk bags, and bags.

IV-3) Membranes, insulation, covers and seals for roofs, tunnels, dumps,ponds, dumps, walls roofing membranes, geomembranes, swimming pools,curtains (shades)/sun-shields, awnings, canopies, wallpaper, foodpacking and wrapping (flexible and solid), medical packaging (flexible &solid), airbags/safety belts, arm- and head rests, carpets, centreconsole, dashboard, cockpits, door, overhead console module, door trim,headliners, interior lighting, interior mirrors, parcel shelf, rearluggage cover, seats, steering column, steering wheel, textiles, andtrunk trim.

V) Films (packaging, dump, laminating, agriculture and horticulture,greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, wastebags, wallpaper, stretch film, raffia, desalination film, batteries, andconnectors.

VI-1) Food packing and wrapping (flexible and solid), bottles.

VI-2) Storage systems such as boxes (crates), luggage, chest, householdboxes, pallets, shelves, tracks, screw boxes, packs, and cans.

VI-3) Cartridges, syringes, medical applications, containers for anytransportation, waste baskets and waste bins, waste bags, bins, dustbins, bin liners, wheely bins, container in general, tanks forwater/used water/chemistry/gas/oil/gasoline/diesel; tank liners, boxes,crates, battery cases, troughs, medical devices such as piston,ophthalmic applications, diagnostic devices, and packing forpharmaceuticals blister.

VII-1) Extrusion coating (photo paper, tetrapack, pipe coating),household articles of any kind (e.g. appliances, thermos bottle/clotheshanger), fastening systems such as plugs, wire and cable clamps,zippers, closures, locks, and snap-closures.

VII-2) Support devices, articles for the leisure time such as sports andfitness devices, gymnastics mats, ski-boots, inline-skates, skis, bigfoot, athletic surfaces (e.g. tennis grounds); screw tops, tops andstoppers for bottles, and cans.

VII-3) Furniture in general, foamed articles (cushions, impactabsorbers), foams, sponges, dish clothes, mats, garden chairs, stadiumseats, tables, couches, toys, building kits (boards/figures/balls),playhouses, slides, and play vehicles.

VII-4) Materials for optical and magnetic data storage.

VII-5) Kitchen ware (eating, drinking, cooking, storing).

VII-6) Boxes for CD's, cassettes and video tapes; DVD electronicarticles, office supplies of any kind (ball-point pens, stamps andink-pads, mouse, shelves, tracks), bottles of any volume and content(drinks, detergents, cosmetics including perfumes), and adhesive tapes.

VII-7) Footwear (shoes/shoe-soles), insoles, spats, adhesives,structural adhesives, food boxes (fruit, vegetables, meat, fish),synthetic paper, labels for bottles, couches, artificial joints (human),printing plates (flexographic), printed circuit boards, and displaytechnologies.

VII-8) Devices of filled polymers (talc, chalk, china clay (kaolin),wollastonite, pigments, carbon black, TiO₂, mica, nanocomposites,dolomite, silicates, glass, asbestos).

Of special interest are compositions comprising as component (a) fibersand nonwovens.

Thus, a further embodiment of the present invention relates to a shapedarticle, in particular a film, pipe, profile, bottle, tank or container,fiber containing a composition as described above.

A further embodiment of the present invention relates to a moldedarticle containing a composition as described above. The molding is inparticular effected by injection, blow, compression, roto-molding orslush-molding or extrusion.

The present invention also relates to a process for reducing the surfaceenergy of organic materials which comprises incorporating into theorganic material at least one compound of the formula I [component b)].

The preferred compounds of the formula I or component (b) respectively,and optionally further additives, in the process for reducing thesurface energy [e.g. increasing the oil and water repellency] of organicmaterials are the same as those described for the composition.

A preferred embodiment of the present invention is also the use of acompound of the formula I [component (b)] as reducer of surface energy[e.g. as oil and water repellency agent] for an organic material.

The preferred compounds of the formula I or component (b) respectively,and optionally further additives, in the use as reducer of surfaceenergy [e.g. increasing the oil and water repellency] of organicmaterials are the same as those described for the composition.

The present invention further provides novel compounds of the formula I

wherein

R₁ is —NO₂, —N═CH—R₄ or

R₂ is —X—R₃,

R₃ is a fluorine containing group,

R₄ is C₁-C₂₅alkyl, C₃-C₂₅alkenyl, unsubstitued or C₁-C₄alkyl substitutedphenyl;

R₅ is hydrogen, —Y—R₇,

R₆ is hydrogen, C₁-C₈alkyl or benzyl,

R₇ is C₁-C₂₅alkyl, C₂-C₂₅alkenyl, unsubstitued or with C₁-C₄alkyl orC₁-C₄alkanoylamino substituted phenyl; unsubstituted or C₁-C₄alkylsubstituted phenylamino;

R₈ is —NO₂, —N═CH—R₄ or

R₉ is hydrogen or —Y—R₇,

R₁₀ is hydrogen, C₁-C₈alkyl or benzyl,

X is

R₁₁ is hydrogen, C₁-C₈alkyl or benzyl,

Y is

Z is C₁-C₂₅alkylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene or

and

R₁₂ and R₁₃ are each independently of one another hydrogen, C₁-C₁₂alkylor phenyl, or R₁₁, and R₁₂ together with the linking carbon atom, form aC₅-C₈cycloalkylidene ring which is unsubstituted or substituted by 1 to3 C₁-C₄alkyl groups.

Of special interest are the compounds of the formula I wherein

R₁ is —NO₂, —N═CH—R₄ or

R₂ is —X—R₃,

R₃ is —CH₂CH₂(CF₂)₇CF₃ or —CH₂CH₂(CF₂)₃CF₃,

R₄ is C₄-C₁₂alkyl, C₄-C₁₂alkenyl, unsubstitued or C₁-C₄alkyl substitutedphenyl;

R₅ is hydrogen, —Y—R₇,

R₆ is hydrogen,

R₇ is C₁-C₈alkyl, C₂-C₈alkenyl, phenyl or phenylamino,

R₈ is —NO₂, —N═CH—R₄ or

R₉ is hydrogen, —Y—R₇,

R₁₀ is hydrogen,

X is

R₁₁ is hydrogen,

Y is

Z is C₄-C₁₂alkylene, 1,3-phenylene, 1,4-phenylene or

and

R₁₂ and R₁₃ are hydrogen.

The preferred meanings of the general symbols in the novel compounds ofthe formula Ia are the same as the preferred meanings of the generalsymbols set out in relation to the compositions of the invention.

The following examples illustrate the invention further. Parts orpercentages relate to weight.

EXAMPLE 1 Preparation of the Compound of the Formula 101

17.8 g (40.0 mmol) of the fluorinated alcohol (Zonyl BA-L) and 4.45 g(44.0 mmol) of triethylamine are dissolved in 50 ml of tetrahydrofuran.4.96 g (20.0 mmol) of 5-nitroisophthaloyl chloride is dissolved in 10 mlof tetrahydrofuran and slowly dropped to the reaction mixture at 0-10°C. under nitrogen atmosphere. A large mass of a white solid is formedand as the reaction becomes difficult to stir, 90 ml of tetrahydrofuranis added. The reaction mixture is stirred at room temperature for 12hours. Diethyl ether (200 ml) is added and the organic phase is washedrepeatedly with 1 N NH₄Cl and water until pH neutral. The organic phaseis dried over magnesium sulfate, filtered and concentrated using avacuum rotary evaporator to give 16.5 g of a yellow solid. The crudesolid is purified by recrystallization in tetrahydrofuran/diethyl etherto give 13.1 g of the compound 101, white solid, m.p. 108-110° C. ¹HNMR: (300 MHz, CDCl₃): δ=9.07 (s, ArH, 2H); 9.00 (s, ArH, 1H); 4.76 (t,J=6.3 Hz, OCH₂CH₂CF₂, 4H); 2.80-2.55 (m, OCH₂CH₂CF₂, 4H).

EXAMPLE 2 Preparation of the Compound of the Formula 102

In an autoclave vessel (100 ml Glass-Camile), 8.50 g (8.00 mmol) of thecompound of the formula 101 [prepared according to Example 1] and 0.50 gof the catalyst (Pd/C, 10% wt) are dissolved in 50 ml of tetrahydrofuranunder inert gas. H₂ gas is then loaded until a pressure of 5 bar isobtained in the vessel. The reaction mixture is stirred for 12 hours at75° C. The reaction mixture is cooled down to room temperature, then thecatalyst is filtered off and the solvent is evaporated using a vacuumrotary evaporator to give 6.85 g of the compound 102, pale yellow solid,m.p. 132-133° C. ¹H NMR: (300 MHz, acetone-d₆): δ=7.95-7.90 (m, ArH,1H); 7.60-7.55 (m, ArH, 2H); 5.31 (br s, NH₂, 2H); 4.68 (t, J=6.0 Hz,OCH₂CH₂CF₂, 4H); 3.00-2.55 (m, OCH₂CH₂CF_(2,)4H).

EXAMPLE 3 Preparation of the Compound of the Formula 103

1.21 g (1.20 mmol) of the compound of the formula 102 [preparedaccording to Example 2] and 0.14 g (1.40 mmol) of triethylamine aredissolved in 30 ml of tetrahydrofuran. 0.14 g (1.20 mmol) of pivaloylchloride is added to the reaction mixture at room temperature undernitrogen atmosphere. The reaction mixture is stirred at room temperaturefor 6 hours. Diethyl ether (80 ml) is added and the organic phase iswashed repeatedly with water until pH neutral. The organic phase isdried over magnesium sulfate, filtered and concentrated using a vacuumrotary evaporator to give 1.20 g of a pale brown wax. The crude productis purified by flash chromatography (hexane/ethyl acetate: 2:1) to give1.10 g of the compound of formula 103, pale yellow wax. ¹H NMR: (300MHz, acetone-d₆): δ=9.09 (br s, NH, 1H); 8.70-8.65 (m, ArH, 2H);8.40-8.30 (m, ArH, 1H); 4.74 (t, J=6.0 Hz, OCH₂CH₂CF₂, 4H); 3.00-2.75(m, OCH₂CH₂CF_(2,)4H); 1.34 (s, tert-butyl, 9H).

EXAMPLE 4 Preparation of the Compound of the Formula 104

1.51 g (1.50 mmol) of the compound of the formula 102 [preparedaccording to Example 2] and 0.18 g (1.80 mmol) of triethylamine aredissolved in 40 ml of tetrahydrofuran. 0.15 g (0.70 mmol) ofterephthaloyl chloride is added to the reaction mixture at roomtemperature under nitrogen atmosphere. The reaction mixture is stirredat room temperature for 12 hours. Ethyl acetate (100 ml) andtetrahydrofuran (50 ml) are added and the organic phase is washedrepeatedly with water and brine until pH neutral. The aqueous phase isdiscarded and the material in suspension in the organic phase isfiltered off to give 0.95 g of the compound of formula 104, white solid,m.p. 160-268° C. ¹H NMR: (300 MHz, tetrahydrofuran-d₈): δ=9.95 (s, NH,2H); 8.80-8.70 (m, ArH, 4H); 8.50-8.40 (m, ArH, 2H); 8.20-8.10 (m, ArH,4H); 4.71 (t, J=6.0 Hz, OCH₂CH₂CF₂, 8H); 2.95-2.70 (m, OCH₂CH₂CF₂, 8H).

EXAMPLE 5 Preparation of the Compound of the Formula 105

1.80 g (1.70 mmol) of the compound of the formula 102 [preparedaccording to Example 2] and 0.21 g (2.10 mmol) of triethylamine aredissolved in 40 ml of tetrahydrofuran. 0.21 g (1.70 mmol) ofphenylisocyanate is added to the reaction mixture at room temperatureunder nitrogen atmosphere. The reaction mixture is stirred at roomtemperature for 24 hours. Diethyl ether (100 ml) is added and theorganic phase is washed repeatedly with 1N NH₄Cl, water and brine untilpH neutral. The organic phase is dried over magnesium sulfate, filteredand concentrated using a vacuum rotary evaporator to give 2.00 g of apale yellow solid. The crude product is purified by recrystallization inethyl acetate to give 0.67 g of the compound of formula 105, whitesolid, m.p. 164-166° C. ¹H NMR: (300 MHz, acetone-d₆): δ=8.58 (br s, NH,1H); 8.55-8.45 (m, ArH, 2H); 8.35-8.25 (m, 1H); 8.25-8.15 (m, 1H);7.65-7.50 (m, ArH, 2H); 7.35-7.20 (m, ArH, 2H); 7.10-6.95 (m, ArH, 1H);4.74 (t, J=6.0 Hz, OCH₂CH₂CF₂, 4H); 3.00-2.70 (m, OCH₂CH₂CF₂, 4H).

EXAMPLE 6 Preparation of the Compound of the Formula 106

2.25 g (2.18 mmol) of the compound of the formula 102 [preparedaccording to Example 2] and 0.27 g (2.62 mmol) of triethylamine aredissolved in 50 ml of tetrahydrofuran. 0.17 g (1.09 mmol) of1,4-phenylenediisocyanate is added to the reaction mixture at roomtemperature under nitrogen atmosphere. The reaction mixture is stirredat room temperature for 24 hours. Water (50 ml) is added and thereaction mixture is stirred for 15 minutes, then the solid was filteredoff and dried in an oven to give the compound of formula 106, whitesolid, m.p.>200° C.

EXAMPLE 7 Preparation of the Compound of the Formula 107

6.92 g (15.6 mmol) of the fluorinated alcohol (Zonyl BA-L) and 2.37 g(23.4 mmol) of triethylamine are dissolved in 40 ml of tetrahydrofuran.3.60 g (15.6 mmol) of 3,5-dinitrobenzoyl chloride is added portionwiseto the reaction mixture at 0-10° C. under nitrogen atmosphere. Thereaction mixture is stirred at room temperature for 12 hours. Diethylether (100 ml) is added and the organic phase is washed repeatedly with1N NH₄Cl and water until pH neutral. The organic phase is dried overmagnesium sulfate, filtered and concentrated using a vacuum rotaryevaporator to give 9.40 g of a yellow solid. The crude product ispurified by flash chromatography (hexane/ethyl acetate: 4:1) to give7.50 g of the compound of formula 107, white solid, m.p. 111-113° C. ¹HNMR: (300 MHz, CDCl₃): δ=9.30-9.25 (m, ArH, 1H); 9.20-9.15 (m, ArH, 2H);4.80 (t, J=6.3 Hz, OCH₂CH₂CF₂, 2H); 2.85-2.60 (m, OCH₂CH₂CF₂, 2H).

EXAMPLE 8 Preparation of the Compound of the Formula 108

18.8 g (71.1 mmol) of the fluorinated alcohol (Fluorochem Limited) and8.63 g (85.3 mmol) of triethylamine are dissolved in 120 ml of drytoluene. 8.82 g (35.6 mmol) of 5-nitroisophthaloyl chloride is slowlyadded portionwise to the reaction mixture at 0-10° C. under nitrogenatmosphere. A large mass of a white solid is formed and as the reactionbecame difficult to stir, 280 ml of dry toluene is added. The reactionmixture is stirred at room temperature for 12 hours. Then water (300 ml)is added, the suspension is stirred for 1 hour and the solid is filteredoff, washed repeatedly with water and dried in an oven to give 14.9 g ofthe compound of formula 108, white solid, m.p. 91-92° C. ¹H NMR: (300MHz, acetone-d₆): δ=9.00 (br s, ArH, 2H); 8.95 (br s, ArH, 1H); 4.83 (t,J=6.0 Hz, OCH₂CH₂CF₂, 4H); 3.05-2.80 (m, OCH₂CH₂CF_(2,)4H).

EXAMPLE 9 Preparation of the Compound of the Formula 109

In an autoclave vessel (100 ml Glass-Camile), 9.80 g (13.9 mmol) of thecompound of the formula 108 [prepared according to Example 8] and 0.80 gof the catalyst (Pd/C, 10% wt) are dissolved in 50 ml of tetrahydrofuranunder inert gas. H₂ gas is then loaded until a pressure of 5 bar isobtained in the vessel. The reaction mixture is stirred for 20 hours at75° C. The reaction mixture is cooled down to room temperature, then thecatalyst is filtered off and the solvent is evaporated using a vacuumrotary evaporator to give 8.00 g of the compound of formula 109, whitesolid, m.p. 131-133° C. ¹H NMR: (300 MHz, tetrahydrofuran-d₈): δ=8.05(br s, ArH, 1H); 7.53 (br s, ArH, 2H); 4.65 (t, J=6.3 Hz, OCH₂CH₂CF₂,4H); 4.00 (br s, NH₂, 2H); 2.75-2.50 (m, OCH₂CH₂CF_(2,)4H).

EXAMPLE 10 Preparation of the Compound of the Formula 110

1.78 g (2.64 mmol) of the compound of the formula 109 [preparedaccording to Example 9] and 0.38 g (3.70 mmol) of triethylamine aredissolved in 25 ml of tetrahydrofuran. 0.32 g (2.64 mmol) of pivaloylchloride is added to the reaction mixture at room temperature undernitrogen atmosphere. The reaction mixture is stirred at room temperaturefor 1 hour. Diethyl ether (80 ml) is added and the organic phase iswashed repeatedly with water until pH neutral. The organic phase isdried over magnesium sulfate, filtered and concentrated using a vacuumrotary evaporator to give 1.85 g of the compound of formula 110, paleyellow solid, m.p. 71-73° C. ¹H NMR: (300 MHz, CDCl₃): δ=8.50-8.40 (m,ArH, 2H); 8.45-8.35 (m, ArH, 1H); 7.56 (br s, NH, 1H); 4.67 (t, J=6.3Hz, OCH₂CH₂CF₂, 4H); 2.75-2.55 (m, OCH₂CH₂CF_(2,)4H); 1.36 (s, tBu, 9H).

EXAMPLE 11 Preparation of the Compound of the Formula 111

1.82 g (2.70 mmol) of the compound of the formula 109 [preparedaccording to Example 9] and 0.33 g (3.24 mmol) of triethylamine aredissolved in 70 ml of tetrahydrofuran. 0.27 g (1.35 mmol) ofterephthaloyl chloride is added to the reaction mixture at roomtemperature under nitrogen atmosphere. The reaction mixture is stirredat room temperature for 2 hours. Ethyl acetate (200 ml) is added and theorganic phase is washed repeatedly with water and brine until pHneutral. The organic phase is dried over magnesium sulfate, filtered andconcentrated using a vacuum rotary evaporator to give 1.90 g of a paleyellow solid. The crude product is purified by flash chromatography(hexane/ethyl acetate: 2:1) to give 1.70 g of the compound of formulaIII, white solid, m.p. 187-223° C. ¹H NMR: (300 MHz, acetone-d₆):δ=10.12 (s, NH, 2H); 8.85-8.80 (m, ArH, 4H); 8.45-8.40 (m, ArH, 2H);8.23 (s, ArH, 4H); 4.77 (t, J=6.0 Hz, OCH₂CH₂CF₂, 8H); 3.00-2.80 (m,OCH₂CH₂CF₂, 8H).

EXAMPLE 12 Preparation of the Compound of the Formula 112

3.40 g (5.05 mmol) of the compound of the formula 109 [preparedaccording to Example 9] and 0.62 g (6.07 mmol) of triethylamine aredissolved in 130 ml of tetrahydrofuran. 0.67 g (2.53 mmol) of5-nitroisophthaloyl chloride is added portionwise to the reactionmixture at room temperature under nitrogen atmosphere. The reactionmixture is stirred at room temperature for 10 hours. Ethyl acetate (300ml) is added and the organic phase is washed repeatedly with water andbrine until pH neutral. The organic phase is dried over magnesiumsulfate, filtered and concentrated using a vacuum rotary evaporator togive 3.80 g of a yellow solid. The crude product is purified by flashchromatography (hexane/ethyl acetate: 3:1) to give 0.90 g of thecompound of formula 112, yellow solid, m.p. 175-184° C. ¹H NMR: (300MHz, acetone-d₆): δ=10.50 (s, NH, 2H); 9.10 (s, ArH, 3H); 8.85-8.80 (m,ArH, 4H); 8.50-8.40 (m, ArH, 2H); 4.78 (t, J=6.0 Hz, OCH₂CH₂CF₂, 8H);3.00-2.80 (m, OCH₂CH₂CF₂, 8H).

EXAMPLE 13 Preparation of the Compound of the Formula 113

1.50 g (2.23 mmol) of the compound of the formula 109 [preparedaccording to Example 9] and 0.25 g (2.46 mmol) of triethylamine aredissolved in 50 ml of tetrahydrofuran. 0.28 g (1.12 mmol) of4,4′-methylene-bis-phenylisocyanate is added to the reaction mixture atroom temperature under nitrogen atmosphere. The reaction mixture isstirred at room temperature for 24 hours. Tetrahydrofuran (50 ml) isadded and the reaction mixture is stirred for 15 minutes, then the solidwas filtered off. The clear colorless mixture is diluted with ethylacetate, washed with water, dried over magnesium sulfate, filtered andconcentrated. The crude material was recrystallized in acetonitrile togive the compound of formula 113, white solid, m.p. 189-191° C. ¹H NMR:(300 MHz, acetone-d₆): δ=8.56 (br s, NH, 2H); 8.52-8.42 (m, ArH, 4H);8.30-8.20 (m, 2H); 8.19 (br s, NH, 2H); 7.55-7.40 (m, ArH, 4H);7.22-7.10 (m, ArH, 4H); 4.73 (t, J=6.0 Hz, OCH₂CH₂CF₂, 8H); 3.92 (s,ArCH₂Ar, 2H); 3.00-2.70 (m, OCH₂CH₂CF₂, 8H).

EXAMPLE 14 Preparation of the Compound of the Formula 114

In an autoclave vessel (100 ml Glass-Camile), 2.30 g (1.51 mmol) of thecompound of the formula 112 [prepared according to Example 12] and 0.25g of the catalyst (Pd/C, 10% wt) are dissolved in 40 ml oftetrahydrofuran under inert gas. H₂ gas is then loaded until a pressureof 5 bar is obtained in the vessel. The reaction mixture is stirred for6 hours at 75° C. The reaction mixture is cooled down to roomtemperature, then the catalyst is filtered off and the solvent isevaporated using a vacuum rotary evaporator to give 2.10 g of thecompound of formula 114, pale yellow solid. ¹H NMR: (300 MHz,acetone-d₆): δ=10.00 (s, NH, 2H); 8.85-8.70 (m, ArH, 4H); 8.45-8.35 (m,ArH, 2H); 7.82 (br s, ArH, 1H); 7.55-7.45 (m, ArH, 2H); 5.26 (br s, NH₂,2H); 4.76 (t, J=6.0 Hz, OCH₂CH₂CF₂, 8H); 3.00-2.75 (m, OCH₂CH₂CF₂, 8H).

EXAMPLE 15 Preparation of the Compound of the Formula 115

1.95 g (1.31 mmol) of the compound of the formula 114 [preparedaccording to Example 14] and 0.16 g (1.56 mmol) of triethylamine aredissolved in 30 ml of tetrahydrofuran. 0.13 g (0.65 mmol) ofterephthaloyl chloride is added to the reaction mixture at roomtemperature under nitrogen atmosphere. The reaction mixture is stirredat room temperature for 5 hours. Water (30 ml) is added and the reactionmixture is stirred for 15 minutes, then the solid is filtered off anddried in an oven to give the compound of formula 115, white solid, m.p.337-347° C. ¹H NMR: ¹H NMR: (300 MHz, tetrahydrofuran-d₈): δ=10.19 (s,NH, 4H); 10.06 (s, NH, 2H); 8.82-8.75 (m, ArH, 8H); 8.72-8.65 (m, ArH,4H); 8.50-8.45 (m, ArH, 4H); 8.45-8.35 (m, ArH, 2H); 8.22-8.18 (m, ArH,4H); 4.72 (t, J=6.0 Hz, OCH₂CH₂CF₂, 16H); 2.95-2.70 (m, OCH₂CH₂CF₂,16H).

EXAMPLE 16 Water and Oil Repellency in Polypropylene

In order to determine the repellency properties of the compounds of theformula I, they are tested according to the following procedure. Thesample preparation is a combination of polypropylene nonwovens and theadditive and a thermal treatment (e.g. 130° C. for 10 minutes), whichenables the migration of the additive to the surface and a propersurface rearrangement of the chemical groups. This extra heat cycle isneeded to melt the compounds of the formula I in order to obtain ahomogeneous redistribution over the surface of the substrate. Anindustrial sample of polypropylene nonwoven, fabric weight: 40 g/m², isdipped into a 1% isopropanol solution of the test compound,simultaneously applying ultrasonic energy for one minute. After that,the sample is dried overnight at room temperature and then two hours at90° C. in an oven. A part of the sample is afterwards annealed for 10minutes at 130° C.

The treated nonwoven samples are evaluated in the water repellency testsimilar to INDA test method 80.8 (99). The wetting behavior of thenonwovens is tested with a series of water/isopropanol mixtures. Theobservation of the wetting behavior is rated from 0 (water wetting, norepellency) to 10 (optimum water repellency). The results are summarizedin Table 1.

TABLE 1 Water repellency Water repellency Example Compound after dryingafter annealing 16a^(a)) — 2 2 16b^(b)) 101 9 10 16c^(b)) 102 8 916d^(b)) 103 9 9 16e^(b)) 104 6 9 16f^(b)) 105 10 10 16g^(b)) 106 7 916h^(b)) 107 7 8 16i^(b)) 111 7 7 16j^(b)) 113 5 5 16k^(b)) 114 6 616l^(b)) 115 5 6 ^(a))Comparative Example. ^(b))Example according to theinvention.

The treated nonwoven samples are evaluated in the oil repellency testsimilar to AATCC test method 118-1997/ISO 14419. This test follows thesame concepts of the already described for water repellency test method,but using, as test solvents, a series of hydrocarbons. The observationof the wetting behavior is rated from 0 (no repellency) to 8 (optimumrepellency). The results are summarized in Table 2.

TABLE 2 Oil repellency Oil repellency Example Compound after dryingafter annealing 16m^(a)) — 0 0 16n^(b)) 101 6 5 16o^(b)) 103 8 816p^(b)) 105 8 8 ^(a))Comparative Example. ^(b))Example according to theinvention.

EXAMPLE 17 Polypropylene Nonwoven Fiber

Compounding: The compound of formula 101 [prepared according to Example1] is heated in an oven at 70° C. until it is completely liquid. Thisliquid is added at 10-20 ml/min to a twin-screw extrusion ofpolypropylene pellets via a heated graduated cylinder using a LeistritzMIC 27/GL-32D twin-screw extruder. The extruder zones are 150°-195° C.with the main screw at 500 RPM and the PP feeder at 200-250 RPM. Themolten polymer and additive exit via a two orifice round die. The moltenmaterial is immediately cooled and solidified in a cold-water trough.The solidified strand is fed into a Conair/Jetro 304 Pelletizer. Thepolypropylene used for the spunbond processing is PP 3155 fromExxonMobil (melt flow rate 36 g/10 min) and PP 3546 from ExxonMobil(melt flow rate 1200 g/10 min) for the meltblown processing.

Alternatively, the compound of formula 101 is made into masterbatches bythose skilled in the technique. The masterbatch at the desired level isthen tumble mixed with the appropriate polypropylene for making spunbondand meltblown nonwovens.

Tumble Mixing The concentrate pellets are let down with additionalpolypropylene pellets and are mixed with a Marion SPS 1224 mixer,resulting in a desired additive concentration by weight.

Spunbond Process Spunbond nonwoven polypropylene fibers are preparedfrom the tumble-mixed additive pellets prepared as above using a 1-meterwide Reicofil II Spunbond Pilot Line, under the following conditions:Extruder temperature of 200-220° C. Screen changer temperature of 205°C. Spin pump speed of 9 rpm. 4,000 Hole spinneret with a temperaturegradient of 223-240° C. Bonder pressure of 260-300 PLI with bondingtemperature of 130-140° C. Cooling air speed of 1700 rpm and suction airspeed of 1500 rpm, and collection take up speed is adjusted to produce anonwoven with a specific basis weight.

Meltblown Process Meltblown polypropylene fibers are also prepared fromthe tumble-mixed additives pellets prepared as above using 24-inchReifenhauser Melt Blowing Pilot Line with Bi-component technology, underthe following conditions: Extruder temperature of 160-240° C. for both A& B extruders. Screen changer temperature of 240° C. Spin pump speed of16 rpm for both A & B extruders. Die temperature gradient of 240° C.Throughput 29.7 kg/h. Suction blower speed of 2000 rpm. Spin belt speedis adjusted to produce a nonwoven with a specific basis weight.

Alternatively: Meltblown polypropylene fibers are also prepared from thetumble-mixed additives pellets prepared as above using a custom-built6-inch Melt Blowing Pilot Line under the following conditions: Extrudertemperature of 175-265° C. Die temperature of 265° C. Throughput 0.49g/h/m (4.44 kg/h). Spin drum speed is adjusted to produce a nonwovenwith a specific basis weight.

The produced nonwoven samples are evaluated on their water/alcoholrepellency behavior similar to INDA standards (International Nonwovenand Disposables Association). The results are summarized in Table 3.

TABLE 3 Example Compound Water repellency 17a^(a)) — 2 17b^(b)) 1% ofcompound 101^(c)) 7 17c^(b)) 2% of compound 101^(c)) 9 ^(a))ComparativeExample. ^(b))Example according to the invention.

1. A composition comprising a) an organic material which is susceptibleto oxidative, thermal or light-induced degradation, and b) at least acompound of the formula I

wherein R₁ is —NO₂, —N═CH—R₄ or R₁ is —NO₂, —N═CH—R₄ or

R₂ is —NO₂, —N═CH—R₄,

or —X—R₃, R₃ is a fluorine containing group, R₄ is C₁-C₂₅alkyl,C₃-C₂₅alkenyl, unsubstitued or C₁-C₄alkyl substituted phenyl; R₅ ishydrogen, Y—R₇,

R₆ is hydrogen, C₁-C₈alkyl or benzyl, R₇ is C₁-C₂₅alkyl, C₂-C₂₅alkenyl,unsubstitued or with C₁-C₄alkyl or C₁-C₄alkanoyl-amino substitutedphenyl; unsubstituted or C₁-C₄alkyl substituted phenylamino; R₈ is —NO₂,—N═CH—R₄ or

R₉ is hydrogen or —Y—R₇,

R₁₀ is hydrogen, C₁-C₈alkyl or benzyl, X is

R₁₁ is hydrogen, C₁-C₈alkyl or benzyl, Y is

Z is C₁-C₂₅alkylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene or

and R₁₂ and R₁₃ are each independently of one another hydrogen,C₁-C₁₂alkyl or phenyl, or R₁₁ and R₁₂ together with the linking carbonatom, form a C₅-C₈cycloalkylidene ring which is unsubstituted orsubstituted by 1 to 3 C₁-C₄alkyl groups.
 2. A composition according toclaim 1, wherein R₂ is —X—R₃, R₃ is C₁-C₂₅fluoroalkyl, X is

and R₁₁ is hydrogen or C₁-C₄alkyl.
 3. A composition according to claim1, wherein R₃ is C₁-C₂₅fluoroalkyl.
 4. A composition according to claim1, wherein R₆ and R₁₀ are hydrogen.
 5. A composition according to claim1, wherein R₇ is C₁-C₁₈alkyl, C₂-C₁₈alkenyl, unsubstitued or withC₁-C₄alkyl or C₁-C₄alkanoylamino substituted phenyl; unsubstituted orC₁-C₄alkyl substituted phenylamino.
 6. A composition according to claim1, wherein R₁₂ and R₁₃ are each independently of one another hydrogen orC₁-C₄alkyl, or R₁₂ and R₁₃ together with the linking carbon atom, form acyclohexylidene ring.
 7. A composition according to claim 1, wherein R₁is —NO₂, —N═CH—R₄ or

R₂ is —NO₂, —N═CH—R₄

or —X—R₃, R₃ is —CH₂CH₂(CF₂)₇CF₃ or —CH₂CH₂(CF₂)₃CF₃, R₄ is C₄-C₁₂alkyl,C₄-C₁₂alkenyl, unsubstitued or C₁-C₄alkyl substituted phenyl; R₅ ishydrogen, —Y—R₇,

R₆ is hydrogen, R₇ is C₁-C₈alkyl, C₂-C₈alkenyl, phenyl or phenylamino,R₈ is —NO₂, —N═CH—R₄ or

R₉ is hydrogen, —Y—R₇,

R₁₀ is hydrogen, X is

R₁₁ is hydrogen, Y is

Z is C₄-C₁₂alkylene, 1,3-phenylene, 1,4-phenylene or

and R₁₂ and R₁₃ are hydrogen.
 8. A composition according to claim 1wherein component (a) is a natural, semi-synthetic or synthetic polymer.9. A composition according to claim 1 wherein component (a) is asynthetic polymer.
 10. A composition according to claim 1 whereincomponent (b) is a fiber or nonwoven.
 11. A composition according toclaim 1 wherein component (b) is present in an amount of from 0.01 to10%, based on the weight of component (a).
 12. A composition accordingto claim 1, comprising in addition, besides components (a) and (b),further additives.
 13. A composition according to claim 12, comprisingas further additives phenolic antioxidants, light-stabilizers and/orprocessing stabilizers.
 14. A compound of the formula I

wherein R₁ is —NO₂, —N═CH—R₄ or

R₂ is —X—R₃, R₃ is a fluorine containing group, R₄ is C₁-C₂₅alkyl,C₃-C₂₅alkenyl, unsubstitued or C₁-C₄alkyl substituted phenyl; R₅ ishydrogen, —Y—R₇,

R₆ is hydrogen, C₁-C₈alkyl or benzyl, R₇ is C₁-C₂₅alkyl, C₂-C₂₅alkenyl,unsubstitued or with C₁-C₄alkyl or C₁-C₄alkanoylamino substitutedphenyl; unsubstituted or C₁-C₄alkyl substituted phenylamino; R₈ is —NO₂,—N═CH—R₄ or

R₉ is hydrogen or —Y—R₇,

R₁₀ is hydrogen, C₁-C₈alkyl or benzyl, X is

R₁₁ is hydrogen, C₁-C₈alkyl or benzyl, Y is

Z is C₁-C₂₅alkylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene or

and R₁₂ and R₁₃ are each independently of one another hydrogen,C₁-C₁₂alkyl or phenyl, or R₁₁ and R₁₂ together with the linking carbonatom, form a C₅-C₈cycloalkylidene ring which is unsubstituted orsubstituted by 1 to 3 C₁-C₄alkyl groups.
 15. A compound according toclaim 14, wherein R₁ is —NO₂, —N═CH—R₄ or

R₂ is —X—R₃, R₃ is —CH₂CH₂(CF₂)₇CF₃ or —CH₂CH₂(CF₂)₃CF₃, R₄ isC₄-C₁₂alkyl, C₄-C₁₂alkenyl, unsubstitued or C₁-C₄alkyl substitutedphenyl; R₅ is hydrogen, —Y—R₇,

R₆ is hydrogen, R₇ is C₁-C₈alkyl, C₂-C₈alkenyl, phenyl or phenylamino,R₈ is —NO₂, —N═CH—R₄ or

R₉ is hydrogen, —Y—R₇,

R₁₀ is hydrogen, X is

R₁₁ is hydrogen, Y is

Z is C₄-C₁₂alkylene, 1,3-phenylene, 1,4-phenylene or

and R₁₂ and R₁₃ are hydrogen.
 16. A process for reducing the surfaceenergy of organic materials which comprises incorporating into theorganic material at least one component (b) according to claim
 1. 17.Use of component (b) according to claim 1 as reducer of surface energyof an organic material.